The　precipitation　of　Fe3O4　particles　and　the　accompanied　formation　of　Fe3O4-wrapped　copper　structure　are　the　main　obstacles　to　copper　recovery　from　the　molten　slag　during　the　pyrometallurgical　smelting　of　copper　concentrates.　Herein,　the　commercial　powdery　pyrite　or　anthracite　is　replaced　with　pyrite–anthracite　pellets　as　the　reductants　to　remove　a　large　amount　of　Fe3O4　particles　in　the　molten　slag,　resulting　in　a　deep　fracture　in　the　Fe3O4-wrapped　copper　microstructure　and　the　full　exposure　of　the　copper　matte　cores.　When　1wt%　composite　pellet　is　used　as　the　reductant,　the　copper　matte　droplets　are　enlarged　greatly　from　25　µm　to　a　size　observable　by　the　naked　eye,　with　the　copper　content　being　enriched　remarkably　from　1.2wt%　to　4.5wt%.　Density　functional　theory　calculation　results　imply　that　the　formation　of　the　Fe3O4-wrapped　copper　structure　is　due　to　the　preferential　adhesion　of　Cu2S　on　the　Fe3O4　particles.　X-ray　photoelectron　spectroscopy,　Fourier　transform　infrared　spectrometer　(FTIR),　and　Raman　spectroscopy　results　all　reveal　that　the　high-efficiency　conversion　of　Fe3O4　to　FeO　can　decrease　the　volume　fraction　of　the　solid　phase　and　promote　the　depolymerization　of　silicate　network　structure.　As　a　consequence,　the　settling　of　copper　matte　droplets　is　enhanced　due　to　the　lowered　slag　viscosity,　contributing　to　the　high　efficiency　of　copper–slag　separation　for　copper　recovery.　The　results　provide　new　insights　into　the　enhanced　in-situ　enrichment　of　copper　from　molten　slag.　©　University　of　Science　and　Technology　Beijing　2024.